Patent GB-1102026-A (GB)
Title: Oil and water repellent substrates
IPC: C08F20/62
Filed: 1965-03-31
Abstract: Polymers suitable for sizing fibrous or porous substrates have a carbon to carbon main chain and contain recurring monovalent saturated perfluorocarbon groups of 4-18 carbon atoms and recurring acyl fluoride, chloride or bromide groups, at least 20% of the weight of the polymer being contributed by the fluorine atoms of the perfluorocarbon groups and at least 0.2% of the weight of the polymer being contributed by the acyl halide groups. The polymers are prepared by copolymerizing (a) an appropriate perfluorocarbon-containing monomer with (b) an acyl halide monomer, and, optionally, (c) other ethylenically unsaturated compounds. Monomers (a) include acrylate, methacrylate and chloroacrylate esters of perfluoroalkane sulphonamido-alkanols, omega(perfluoroalkyl)-alkanols or 1,1,3 - trihydroperfluoroalkanols; 1,1 - dihydroperfluoroalkyl - acrylamides and -vinyl ethers; and vinyl or allyl perfluoroalkyl ketones.  Monomers (b) specified are the chloride, fluoride and bromide of acrylic or maleic acid, and the chlorides of methacrylic, cinnamic, buten-3-oic, fumaric, itaconic, sorbic, citraconic and p-vinyl benzoic acids.  Optional monomers (c) include ethylene, vinyl esters, vinyl and vinylidene halides, acrylonitrile, methacrylonitrile, vinylidene cyanide, styrene and its alkyl and halogen derivatives, alkyl and epoxy alkyl esters of acrylic, methacrylic or chloroacrylic acid, vinylheterocyclic compounds, vinyl alkyl ethers and ketones, butadiene, isoprene, chloroprene and fluoroprene.  Polymerization is generally effected in bulk or in solution using, as solvent, halo-hydrocarbons, benzene or butyl acetate.  In Examples, benzoyl peroxide is used as catalyst and, in some cases, homopolymers of the monomer (a) are also prepared.ALSO:Fibrous or porous substrates having no active hydrogen on the surface thereof are sized with a co-polymer of (a) an ethylenically unsaturated compound containing a monovalent, saturated C4 - C18 perfluorocarbon group, (b) an ethylenically unsaturated compound containing an acyl fluoride, chloride or bromide group and, optionally, (c) another ethylenically unsaturated copolymerisable compound, at least 20% of the weight of the polymer being contributed by the fluorine atoms of component (a) and at least 0.2% of the weight of the polymer being contributed by acyl halide groups, said substrate thereby being rendered durably oil and water repellent. Suitable substrates which can be sized include textile fabrics derived from glass fibres and synthetic fibres, e.g. acrylic, polyester, Saran (registered Trade Mark), nytril and vinyl olefin fibres.  Sizing can be effected by spraying, brushing or padding using solutions or dispersions of the polymers in inert organic solvents, e.g. trichlorofluoromethane, 1, 1, 2-trichloro- 1, 2, 2-trifluoroethane, benzene, benzotrifluoride, xylene hexafluoride, 1, 1, 1-trichloroethane and butyl acetate; the solvent may contain a small proportion of dimethylaniline.  The substrate may also be treated, separately or simultaneously, with one or more conventional finishes, e.g. with mildew preventives, moth resisting agents, modified crease resistant resins, lubricants, softeners, sizes, flame retardants, antistatic agents, dye fixatives and water repellents (all unspecified).  The treated fabrics are cured by heating, e.g. at 130 DEG C for 5 min.  In Examples, the polymers used are prepared by copolymerising (a) monomers of formula C8 C17 SO2 N(C3H7) C2 H4 O2C CH=CH2, C8 F17 SO2 N(CH3) C11 H22 O2 CCH=CH2, C7 F15 CH2 O2 CC(CH3)=CH2, C7 F15 C3 H6 O2 CC(CH3)=CH2 or C8 F17 SO2 N(CH3) C11 H22 O2 CC(CH3) = CH2 with (b) acrylyl chloride or methacrylyl chloride and, optionally, (c) 2-ethylhexyl acrylate or octadecyl methacrylate. The treated substrates can be used, for example as apparel upholstery, draperies, carpeting, bags, containers, luggage, hand-bags, shoes and jackets.